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SKT3013 SUZALIZA

I. Uniqueness principle
II. Diagonal effect
III. Inert-pair effect
 SKT3013 SUZALIZA

edited 2019_Dr. Suzaliza

 PERIODIC TRENDS OF THE ELEMENTS
TKT2013 noorshida mohd ali
SKT3013 SUZALIZA

❖The way certain properties (chemical and physical) of elements

vary according to their location on the periodic table
❖Some variations in:
Electronegativity increases

Electron affinity increases

Ionization energy increases
Effective nuclear charge decreases
Electronegativity decreases

Effective nuclear charge increases

Electron affinity decreases

Ionization energy decrease

Atomic radius increase

Ionic radius increase

Atomic radius decreases

Ionic radius decreases

 SKT3013 SUZALIZA
edited 2019_Dr. Suzaliza

Electronegativity is an atom's tendency to attract electrons to itself in a

chemical bond. https://www.khanacademy.org/science/biology/chemistry--of-
life/chemical-bonds-and-reactions/v/electronegativity-trends

Electron affinityThe energy change that occurs when an electron is

accepted by an atom in the gaseous state to form an anion.
The greater the attraction between an atom and an added electron, the
more negative the atom’s electron affinity will be.

https://www.khanacademy.org/science/chemistry/periodic-
table/periodic-table-trends-bonding/v/electron-affinity
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Uniqueness principle

Li Be B C N O F Ne

The chemistry of the second-period elements

(Li, Be, B, C, N, O, F, Ne) are significantly different from
other elements in their respective groups
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Uniqueness principle

Li Be B C N O F Ne

Na M Al Si P S Cl Ar
g

Second element in each group

(Na, Mg, Al, Si, P, S, Cl, Ar) are more representative
(lebih mewakili sifat kumpulan)
Uniqueness principle
TKT2013 noorshida mohd ali
SKT3013 SUZALIZA

Li Be B C N O F Ne

Why the first elements of the groups are different from

their congeners (elements of the same group)?

a) The small size of the elements leading to a high polarizing power

and a high degree of covalent character in their compounds
(Covalent character :The partial sharing of electrons between atoms that
have an ionic bond)
b) The greater probability of  bonds (p-p)
c) The lack of availability of the d orbitals
a) Covalent character
b) Probability of  bonds
 SKT3013 SUZALIZA
c) The lack of availability of the d orbitals

edited 2019_Dr. Suzaliza

 TKT2013 noorshida mohd ali
SKT3013 SUZALIZA

Small size of the first elements

SIZE EFFECT LEADS TO:

1)Change in electron affinities

The smaller the atom is, the closer the outermost shell is; therefore,
it is a stronger attraction between the nucleus and the incoming
electron. That means the electron affinity is higher for smaller
atoms.
X (g) + ē X-(g)

Electrons added to these small atom, experience more electron

repulsions
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Higher Electron Affinities, an atom more easily accept electron

Lower electron Affinities, an atom more difficult to accept electron
Electron affinity decreases Electron affinity increases
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2) Charge densities
 SKT3013 SUZALIZA
3) Enhanced degrees of covalent character in their compounds
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ali

The first electron affinities of the halogens

edited 2019_Dr. Suzaliza

 SKT3013 SUZALIZA

Why does chlorine have a higher electron

affinity than fluorine?
1. Down a group, electron affinity typically decreases. This is
because the atomic radius increases down a group. The
electron gained ends up in the outermost shell. It is farther
away from the nucleus and thus feels a weaker attraction.
Less energy is released.
2. However, there are EXCEPTIONS. Fluorine, which is higher up
the group then chlorine, has a lower electron affinity.
3. This is because the electrons in the outermost shell of a
fluorine atom are closer together. The electron gained also
feels a great amount of repulsion from the electrons originally
in the outermost shell.
4. Energy is required to keep the gained electron in the shell,
causing fluorine to have a smaller electron affinity than
chlorine.
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SKT3013 SUZALIZA

GROUP 1 (ALKALINE METALS) : Li, Na, K, Rb, Cs, Fr

Lithium behaves differently than others
1. Small size
2. High charge density of cation allow it to polarize nearby anion –
allows a large degree of covalency in its bond and less ionic
3.Less soluble in water and more soluble in polar organic solvents
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1) Small lithium cation get very close to larger, more diffuse or

filled electron cloud of chloride ion.

2) Electron cloud of chloride ion is distorted or polarized by lithium ion

3) This distortion makes overlap between two ions. Orbital overlap and
sharing electron between two species – characteristic of a covalent bond
overlap between the valence orbitals in Li+ (empty 2s) and Cl- (filled 3p)
is increased
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SKT3013 SUZALIZA
Bond energies increase
Weakness of the fluorine – fluorine bond

1. Different in atomic size; distance between Fluorine atoms in F2(g) CLOSER

compared to Chlorine atoms in Cl2(g)

2. Lone pairs of electrons on adjacent fluorine atoms repel each other

(increase repulsion )

3. Weakening the F-F bond in F2 molecule

SKT3013 SUZALIZA
Increased  bonding in the first element
SKT3013 SUZALIZA
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SKT3013 SUZALIZA

Increased  bonding in the first element

• Due to small size, increase  bond formation among themselves and with
other elements (capable of forming strong double and triple bond)

•  bonds involve parallel overlap between for example two p orbitals

( bonding can occur using d orbitals and antibonding molecular orbitals
of some molecules)

• Utilizing  bond than  bond :

C C C O N NC C O O C OC C
• Parallel orbital overlap or  bonding is more effective in smaller first
elements for example carbon than larger congeners, silicon
SKT3013 SUZALIZA
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SKT3013 SUZALIZA

Lack of availability of d orbitals in the first elements

The lighter elements lack availability of d orbitals and therefore cannot
form compounds with expanded octets
SiF62-
CF4
 SKT3013 SUZALIZA

The heavier elements have availability of d orbitals and therefore ABLE

to form compounds with expanded octets
 SKT3013 SUZALIZA

edited 2019_Dr. Suzaliza

 TKT2013 noorshida mohd ali

Diagonal effect
DIAGONAL RELATIONSHIPS exists between the chemistry of the first
member of a group and the second member of the next group

• Similarities between pairs 1 2 13 14

of elements in different
groups and periods of the
periodic table
Phenomenon happens :
1) small ionic size
Li Be B
2) closeness of the charge
densities of their cations
(charge density = charge
of an ion divided by its Mg Al Si
radius : charge nm-1)
3) electronegativity
edited 2019_Dr. Suzaliza
Diagonal Effect
 TKT2013 noorshida mohd ali

Diagonal effect
1 2 13 14

Li Be B C
Charge of ion +1 +2 +3 +4
Ionic radius, Å 0.73 0.41 0.25 0.29
Charge density 1.4 4.9 12 14
Electronegativity
1.0 1.5 2.0 2.5
Na Mg Al Si
Charge of ion +1 +2 +3 +4
Ionic radius, Å 1.13 0.71 0.53 0.40
Charge density 0.88 2.8 5.7 10
Electronegativity
0.9 1.2 1.5 1.8

edited 2019_Dr. Suzaliza

 TKT2013 noorshida mohd ali

Diagonal effect
•Ionic radius of Be2+ (0.41Å) is more
similar to Al3+ (0.53Å) than Mg2+
(0.71Å)
•High charge density of Al3+ ion 1 2 13 14
(5.7) and Be2+ ion (4.9)
•Same electronegativity (1.5)
•Be-X and Al-X : covalent character
•Its small size & high charge density
of cation Be2+ and Al3+ allow them Li Be B
to polarize the electron cloud of 0.41Å
anion (X atom in M-X bond) to give 4.9
additional covalent character
▪AlH3 resembles BeH2 in its
Mg Al Si
properties (example of the diagonal 0.71Å 0.53Å
relationship) 2.8 5.7

edited 2019_Dr. Suzaliza

 TKT2013 noorshida mohd ali
SKT3013 SUZALIZA

Inert-pair effect
Phenomenon of electrons remaining paired in valence shell

Major reasons for this effect:

1.Reluctance of the s-electron of the valance shell to take part in
bonding. 4s, 5s and 6s electrons experience larger effective nuclear
charge than expected cause them more difficult to ionize
2.Occurs due to poor or ineffective shielding of the ns2 (Electrons of
the valance shells by intervening d and f electrons)
3.Inert pair effects increases down the group.
4.The lower elements of the group exhibit lower oxidation states.
5.Increase in atomic size and bond distance cause lower bond
energies
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SKT3013 SUZALIZA

Inert-pair effect
1. Get closer to the bottom of the group (heavier elements –
increasing tendency s2 pair not to be used in the bonding / left
unchanged)

2. Valence electrons in an s orbital are more tightly bound are of

higher energy than electrons in p orbitals and therefore less likely
to be involved in bonding.

3. Electrons closer to the nucleus – difficult to remove the heavier

the element the greater this effect
 TKT2013 noorshida mohd ali
SKT3013 SUZALIZA
Inert-pair effect in Group 13

• The +1 oxidation state of TlI is the most stable

• TlIII compounds comparatively rare.
• The stability increases in the following sequence: AlI < GaI < InI < TlI
• All four elements (Al, Ga, In, Tl) give trivalent compounds(+3) but
the univalent state (+1) becomes increasingly important for Ga, In
and Tl
• Valence ns2 electrons of metallic elements : In, Tl, Sn, Pb, Sb, Bi
and Po are less reactive than expected.
• Inert ns2 pairs mean oxidation state is 2 less than the expected
group valence for the heavier elements of groups 13, 14, 15 and
16.

In [Kr] 4d10 5s2 5p1

Sb [Kr] 4d10 5s2 5p3
Pb [Xe] 4f¹⁴ 5d¹⁰ 6s² 6p²
Tl [Xe] 4f14 5d10 6s2 6p1
Bi [Xe] 4f14 5d10 6s2 6p3